Perfluoro cycloalkyl acrylates

ABSTRACT

This invention relates to novel fluorinated acrylic monomers and polymers thereof and also to a novel method or approach for preparing certain of said monomers and polymers, together with the provision of certain novel intermediates produced thereby.

United States Patent Field of Search ..260/486 H Anello et al. 51 Mar.27, 1973 PERFLUORO CYCLOALKYL [56] References Cited ACRYLATES UNITEDSTATES PATENTS [75] Inventors: Louis Gene Anello, Basking Rodge;

' Ri Sweeney Randolph 3,384,628 5/1968 Pittman et al. ..260/486 HTownship, Dover, both of NJ. i J Primary Examiner-l-lenry R. J iles [73]Asslgnee' 2 Corporahon New Assistant ExaminerPaul J. Killos orAttorney-lrving N. Simmons [22] Filed: June 8, 1970 21 Appl. No.: 57,006[57] ABSTRACT This invention relates to novel fluorinated acrylicRelated Apphcahon Data monomers and polymers thereof and also to a novel[62] Division of Ser. No. 466,831,.lune 24, 1967, Pat. No. method orapproach for preparing certain of said monomers and polymers, togetherwith the provision of certain novel intermediates produced thereby.'[52] 0.8. CI. ..260/486 H 51 Int. Cl ..C01c 69/52 10 Claims, N0 DrawmgsPERFLUORO CYCLOALKYL ACRYLATES This application is a division ofapplication Ser. No. 466,831, filed June 24, 1967, now U.S. Pat. No.3,520,863.

Polymers prepared from the monoesters of acrylic acid and itsderivatives have been long recognized as thermoplastic materials whoseutility is both wide and varied. For example, acrylic polymers have beensuccessfully employed as aircraft components, internally illuminatedcommercial signs, vending machine parts, windows, dials, safety shields,motor-boat deck hatches, shoe heels, piano and organ keys, industrialhousings, etc. in addition, acrylic polymers, particularlyfluorine-containing acrylic polymers, are susceptible to vulcanizationto yield tough, stable polymers suitable for use as gasket material andalso as tenacious coating materials. Fluorine-containing acrylicpolymers are also known to be useful to impart oleophobic andhydrophobic finishes to various materials, such as cotton cloth or woolfabric.

it has generally been observed that the higher the fluorine content ofsuch acrylic materials relative to its molecular weight the greater willbe the enhancement of the oleophobic and/or hydrophobic propertiesimparted to the fabric materials which are coated.

Acrylic monomers are conventionally prepared by the esterification ofacrylic acid or equivalent with an alcohol. Previously knownfluorine-containing acrylic monomers and polymers are characterized bythe presence of at least one CH group in the alcoholic residue portionof the molecule. The preparation of very highly fluorinated acrylicmonomers and polymers, not possessing at least one -CH,-- group asdescribed above, has not been considered feasible due to the expectedinstability of the resulting highly fluorinated molecule and also due tothe well-known instability of perfluorinated alcohols and the resultinginability to form the corresponding perfluorinated ester derivativesthrough the conventional route.

It is accordingly an object of this invention to provide a novel classof fluorine-containing acrylic monomers and polymers characterized bythe absence of --CH groups in what would be considered the alcoholicresidue portion of the molecule.

It is another object of the invention to provide a novel class offluorine-containing acrylic monomers and polymers possessing a higherfluorine content, relative to the molecular weight of the compound, thanhas been provided heretofore.

A preferred object of the invention is to provide a novel class ofacrylic monomers and polymers characterized by being perfluorinated inwhat would be considered the alcoholic residue portion of the molecule.

Still another object of the invention is to provide a novel process orapproach capable of producing the preferred class of perfluorinatedacrylic monomers and polymers described in the above paragraph.

Another object of the invention is to provide certain novel intermediatecompounds which may readily be converted to the preferred class of novelperfluorinated acrylic monomers and subsequently to the novelperfluorinated acrylic polymers of the invention as described above.

Other objects and advantages of the invention will become apparent fromthe following description and from the examples, which are to be takenas illustrative and not limiting.

In the following and foregoing discussion of the invention it isintended that the term acrylic be understood to comprehendmethyl-substituted acrylic, i.e. methacrylic as well as acrylic.Additionally, any reference to perfluorinated acrylic, or perfluorinatedacrylate, is intended to refer to an acrylictype molecule in which thenon-acid residue portion of the molecule, i.e. what would be thealcoholic residue portion of the molecule (whether or not such moleculecan or is formed by esterification with the alcohol), is that which isperfluorinated.

The novel fluorine-containing acrylic monomers of the invention may berepresented by the formula:

wherein R, is a perfluorinated alkylene radical containing from two tofive carbon atoms, X is a member selected from the group consisting of Hand F and Y is a member selected from the group consisting of H and CHThe perfluorinated alkylene radical R,, together with the carbon atom towhich the X member is attached, form a cycloaliphatic moiety. Thepreferred carbon content for the R, radical is four to five carbonatoms. As pointed out hereinbefore, the perfluorinated acrylic compoundsconstitute a preferred species of the invention. This preferred speciesis represented in the above formula when X is F. Another preferredspecies is represented in the above formula by those compounds wherein Yis H. This is because the incorporation of a CH group into the moleculein place of an H group reduces the fluorine content relative to thecompounds molecular weight. Illustrative compounds within the scope ofthe invention include the following:

perfluorocyclopropyl acrylate perfluorocyclobutyl acrylateperfluorocyclopentyl acrylate perfluorocyclohexyl acrylateperfluorocyclobutyl methacrylate perfluorocyclohexyl methacrylatel-hydroperfluorocyclopropyl methacrylate l-hydroperfluorocyclobutylacrylate l-hydroperfluorocyclopentyl acrylate 1-hydroperfluorocyclohexylacrylate l-hydroperfluorocyclopentyl methacrylate Those acrylic monomersof the invention wherein X is H may be prepared by conventionalesterification, i.e. by reacting the appropriate alcohol, particularly al-hydroperfluorocycloalkanol,' with acrylic acid or equivalent. Thel-hydroperfluorocycloalkanol starting materials may be prepared byreducing the corresponding perfluorinated cycloalkanone with sodiumborohydride, in the presence of an inert polar solvent, at temperaturesin the range of about 20 C., as substantially described and illustratedin co-pending, commonly assigned application of Louis G. Anello andRichard F. Sweeney, entitled Novel Halogenated Alcohol Compositions,Ser. No. 424,827, filed Jan. 1 l, 1965. The perfluorinatedcycloalkanones, which are used as starting materials for preparing thel-hydroperfluorocycloalkanols and which also are used as startingmaterials for preparing certain novel intermediates hereinafter to bedescribed, may be prepared by reacting perhalogenated cycloalkanones, inwhich all the halogen atoms are members selected from the groupconsisting of chlorine and fluorine, there being present one or morechlorine atoms each of which is attached to a carbon atom which is in aposition alpha to a ketone group, there also being present one or morefluorine atoms; with an inorganic metal fluoride, such as KF, CsF, UPand AgF in the presence of an inert polar solvent. This procedure issubstantially described and illustrated in copending, commonly assignedapplication of Louis G. Anello and Richard F. Sweeney, entitledPreparation of Perfluorinated Ketones," Ser. No. 427,484, filed Jan. 22,1965.

The perfluorinated acrylic monomers cannot be prepared in such a mannerdue to the instability of the corresponding perfluorinated alcohols. Wehave found that the perfluorinated acrylic monomers may readily beprepared by reacting acrylyl chloride or methacrylyl chloride withcertain ZF adducts of the corresponding perfluorinated cycloalkanones,wherein Z may be a member selected from the group consisting of K, Cs,Ag and Rb. The ZF adducts are stable compounds over a wide range ofconditions and may be represented by the following formula:

It! (I wherein R, is a perfluorinated alkylene group containing at leasttwo carbon atoms and Z is as defined above. The perfluorinatedcycloalkanone starting material may be prepared as described supra. TheZF adducts may be readily prepared by simply stirring a mixture of thedesired ketone with the fluoride of the desired Z element for a shortperiod of time. Acrylyl chloride and methacrylyl chloride were the onlyacrylic reactants found to be capable of effectively forming thecorresponding acrylic monomers from the above described ZF adducts.

Polymerization of the fluorine-containing acrylic monomers of theinvention may be effected by conventional methods, such as bulkpolymerization, emulsion polymerization and solution polymerizationtechniques. Polymers so formed are characterized by containing thefollowing recurring ester units:

wherein R,, X and Y are as defined previously. These recurring units maybe present in homopolymers in which case they are the only repetitiveunits present, or they may be present in copolymers, or otherheteropolymers such as terpolymers, in which case these units may beinterspersed with units derived from other polymerizable unsaturatedmonomers. The homopolymeric products are thermoplastic and, depending onthe molecular weight, vary from soft rubbery compositions to sticky,adhesive-like materials. These polymers are stable, flame resistant,insoluble in hydrocarbon solvents, such as benzene, xylene and solublein certain fluorocarbons, such as trifluoroethyl trifiuoroacetate.Homopolymers of the novel fluorinecontaining acrylic monomers of theinvention, when utilized as fiber impregnators, impart good oleophobicand hydrophobic properties to such materials. The homopolymers also canbe used to cast flexible, transparent, thermoplastic films, which can beused for wrapping and protective purposes. Coand heteropolymericproducts will, of course, reflect properties contributed by the coorheteromonomer(s) and also the effects of cross-linking. Depending uponthe nature of the particular copolymerizable monomer(s) employed, theymay be hard infusible thermosetting type resins, useful as structuralcomponents for a variety of purposes for which prior art acrylicpolymers have been employed, a number of which have been mentionedheretofore. Suitable polymerizable comonomers include the ethylenicallyunsaturated monomers well-known to the art, such as the vinyl compounds,e.g., vinyl esters, vinyl halides, some specific examples being vinylisopropyl sulfone, vinylidene dichloride and N-vinyl urea; olefiniccompounds, such as ethylene, propylene, isobutylene, butadiene andisoprene; aromatic compounds containing olefinic unsaturated groups,such as styrene and alphamethyl styrene; other acrylic compoundsincluding dissimilar fluorinated acrylic monomers in accordance with thedescription of this invention, other halogenated acrylates, acrylic acidamides and acrylic acid nitriles; other unsaturated acid esters, such asmethyl crotonate, methyl maleate, diethyl fumarate and a variety ofother unsaturated compounds, such as unsaturated ketones, e.g., alkylvinyl ketones and the like. Modifiers, such as mercaptans, may be usedto decrease the molecular weight of the polymeric products.

The various methods for preparing the intermediates, monomers andpolymers of the invention and preferred modes of operation will now bediscussed in more detail by the indicated headings.

PREPARATION OF THE 1- HYDROPERFLUORINATED ACRYLIC MONOMERS Thel-hydroperfluorinated acrylic monomers are prepared by reacting thedesired alcohol, as indicated heretofor, with an acrylic compound of theformula:

wherein Y is a member selected from the group consisting of H and CH andM is a member selected from the group consisting ofCl, OH and OCH Theacrylic reactant may also be employed in the form of its anhydride whichmay be used in situ by reacting a mixture of glacial acrylic acid andperfluoroacetic anhydride with the alcohol reactant at below about roomtemperature. In the preferred mode of operation, the acrylic reactant isemployed as the acid chloride, i.e., as acrylyl chloride or methacrylylchloride. When the acid chloride is employed as the acrylic reactant, itis desirable to employ an acid acceptor, e.g., pyridine or quinoline, inorder to minimize undesirable formation of the correspondingl-hydroperfluorocycloalkyl-B-chloropropionate as byproduct. In the eventthe free acid is employed as the acrylic reactant, it is desirable toemploy an acid catalyst, e.g., a mineral acid, such as H in order topromote esterification between the alcohol and the acid.

The molar ratio of the reactants is not critical and from about 0.1 moleto about moles alcohol reactant per mole acrylic reactant may beemployed to secure the desired reaction product. In order to securehighest yields, however, a substantially stoichiometric molar ratioshould be employed, Le, a mole ratio of about 1:1.

The reaction proceeds quite smoothly in the absence of a solvent. Asuitable solvent, if desired however, may be employed to serve as adiluent and to facilitate the reaction at elevated temperatures.Generally speaking, any solvent may be employed provided it is inertunder the conditions of the reaction and provided, of course, that it isa solvent for the reactants. Illustrative suitable solvents include:benzene, pyridine, quinoline, nitrobenzene, dimethyl aniline,trifluoroacetic acid, Decalin and 1,1 ,2-trifluoro-l,2,2-trichloroethane.

In order to minimize reaction time, any of the well known esterificationcatalysts, such as pyridine, quinoline, trifluoroacetic acid, p-toluenesulfonic acid, phosphonic acid, sulfuric acid and cupric chloride may beemployed. The amount of catalyst is not critical and may range fromabout 1.0 to 200 percent by weight based on the amount of alcoholreactant charged. In preferred operation, either pyridine or quinolineis employed since each acts both as a solvent and a catalyst whenacrylyl chloride or methacrylyl chloride is used. Additionally, due totheir low boiling points they may be readily separated from the reactionproduct by simple distillation. Generally, the amount of pyridine orquinoline charged to the reaction mixture is about 0.10 to 2.00 parts,preferably 0.5 to 1:5 parts, per part alcohol reactant charged.

The reaction temperature may vary over a wide range, i.e., from belowroom temperature up to the boiling point of the reaction mixture.Normally a temperature selected from about room temperature to 100 C. isutilized with a mild agitation of the reaction mixture. When theanhydride form of acrylic acid is employed, the reaction mixture ispreferably maintained at about room temperature, say between about 10-30C. and still preferably below about room temperature.

In all embodiments, the esteriflcation reaction is preferably run in thepresence of a small amount of a conventional polymerization inhibitor,such as hydroquinone, a-pinene and p-tertiarybutyl catechol, in order toavoid undesirable premature polymerization which may take place to someextent, particularly at more elevated temperatures.

Reaction times will depend upon the reactivity of the acrylic reactantchosen, the catalyst used, if any, and other variables, such astemperature. Substantial yields of product may be formed in a periodfrom about 30 minutes to several hours.

Recovery and purification of the resulting ester products may beeffected by employing conventional procedures, such as solventextraction, a series of water washing steps, or ordinary distillation.

In the following examples, parts are by weight unless otherwiseindicated.

EXAMPLE 1 To a three-necked 100 ml. flask, fitted with a stirrer, refluxcondenser, thermometer and dropping funnel were added 44 g. (0.16 mole)of l-hydroperfluorocyclohexanol (b.p. 108 C.), 1.0 g. CuCl and 0.1 g. ofhydroquinone. To this mixture were rapidly added 30 g. (0.33 mole) ofacrylyl chloride. The temperature of the resulting mixture was raised toC. and was maintained between 75-80 C., with stirring, for approximately10 hours. At the end of this period the resulting product mixture wasfractionally distilled to give 17 g. (0.046 mole, 31 percent yield) of1- hydroperfluorocyclohexyl-B-chloropropionate, a water-white liquid,b.p. 68 C./10 mm. and 29 g. (0.087 mole, 58 percent yield) of awater-white liquid identified as l-hydroperfluorocyclohexyl acrylate,b.p. 5152 C./35 mm. The latter compound exhibited the typical fruityodor characteristic of esters. Analysis: Calculated for-C H F O F,56.89; H, 1.20. Found: F, 58.0; H, 1.40. Infrared spectrographicanalysis of this compound showed peaks consistent with the expectedstructure.

EXAMPLE 2 To a cold solution of 25.4 g. (0.091 mole) oflhydroperfluorocyclohexanol (b.p. 108 C.), 11.4 g. (0.091 mole) ofnitrobenzene, 11.7 g. (0.091 mole) of quinoline and 0.1 g. ofhydroquinone contained in a three-necked ml. flask, equipped with astirrer, dropping funnel, thermometer and water-cooled condenser, wererapidly added 8.2 g. (0.091 mole) of acrylyl chloride. An exothermicreaction took place. The temperature in the reaction vessel reached amaximum of about 67 C. and then was allowed to cool slowly to about 25C. over a period of about one hour. After the cooling period, theresulting slurry was fractionally distilled to give 20 g. (0.06 mole, 66percent yield) of a water-white liquid, b.p. 5152 C./35 mm. identifiedas l-hydroperfluorocyclohexyl acrylate. The infrared spectrum of thiscompound was identical to the infrared spectrum of the compoundof thesame name produced in Example 1.

EXAMPLE 3 To a three-necked 100 m1. flask, fitted with a stirrer, refluxcondenser, thermometer and dropping funnel, were added 30 g. (0.33 mole)of acrylyl chloride, 1 g. CuCl and 0.1 g. hydroquinone. To this mixturewere rapidly added 39 g. (0.17 mole) of l-hydroperfluorocyclopentanol(b.p. 8788 C.). The temperature of the resulting mixture was raised to75 C. and main- EXAMPLE 4 To a cold solution of 48 g. (0.21 mole) of 1-hydroperfluorocyclopentanol, 28 g. (0.23 mole) of nitrobenzene, 28 g.(0.22 mole) of quinoline and 0.1 g. hydroquinone contained in athree-necked 250 ml. flask, fitted with a stirrer, thermometer, refluxcondenser and dropping funnel, were rapidly added 18.8 g. (0.208 mole)of acrylyl chloride. The reaction flask contents were cooled to controlexotherm so that the temperature was maintained at about 55 C. When theexothermic reaction was complete, the flask contents were heated toabout 60 C. and maintained at that temperature for a period of about 2hours. At the end of this period the resulting slurry was transferred toa 250 ml. flask and distilled. From the distillation there wererecovered about 30 g. ofcrude l-hydroperfluorocyclopentyl acrylate.Refractionation gave 20 g. (0.07 mole, 33% yield) of1-hydroperfluorocyclopentyl acrylatc, h.p. 57-6l C./60 mm.Identification was confirmed by infrared spectrographic analysis againstthe spectrum of the compound of the same name prepared in Example 3.

EXAMPLES 5-8 The procedure of Example 1 is repeated in identicalapparatus, excepting that starting materials, solvents, catalysts andend products are varied as indicated in the following table.

TABLE 1 Starting Acrylic Example material reactant Solvent Catalyst 5l-hydroperfluoroacrylyl pyridine pyridine cyclopropanol chloride 6l-hydroperfluoroacrylyl benzene pyridine cyclobutanol chloride 7l-hydroperfluoromethacrylyl trifluorocupric cyclobutanol chloride aceticacid chloride 8 lhydroperfluoro methacrylyl dimethyl dimethylcyclopentanol chloride aniline aniline PREPARATION OF THE ZF ADDUCTINTERMEDIATES OF PERFLUOROCYLCOALKANONES The ZF adducts of theperfluorinated ring ketones, as defined hereinbefore, are preparedsimply by stirring a mixture of the fluoride of the desired Z elementand the selected perfluorocyclic ketone for a short period of time.

The reaction is preferably carried out under essentially anhydrousconditions, since the presence of water in the reaction mixture willlead to the formation of the corresponding ketone hydrates, as disclosedin copending, commonly assigned application of Louis G. Anello andRichard F. Sweeney, Ser. No. 420,154, filed Dec. 21, 1964, and thusresult in reduced yields of the desired ZF adducts.

Thus, the ZF reactant should be used in anhydrous form. Commerciallyavailable anhydrous KF, for example, is suitable, however, even betterresults can be obtained by further drying such material, such as byheating under vacuum at 150 C. for a period of about 2-16 hours.

The reaction can be effected without the use of any solvent, in whichcase the perfluoroketone reactant is added directly to the ZF reactant,preferably under pressure. In a preferred embodiment, however, a sol- 5vent, which will not react with the reactants, is employed in an amountsufficient to afford an easily stirred suspension of the ZF reactant.For reasons indicated above, the solvent, if employed, should beanhydrous and for best results should be freshly distilled. Suitablesolvents will readily occur to those of ordinary skill in the art andinclude a number of inert polar solvents, such as acetonitrile,tetramethylene sulfone, diglyme, butyrolactone, dimethylformamide andnitrobenzene. Reagent grade acetonitrile, which has been freshlydistilled from P 0 has been found to be particularly satisfactory. If asolvent is used, it should be present in an amount sufficient to affordan easily stirred suspension of the ZF reactant. Normally this isaccomplished by'providing about 3-6 moles of solvent per mole of ZFreactant. Large excesses of solvent over this range will not adverselyaffect the reaction but will complicate purification and recoveryprocedures.

Mixtures of virtually any proportions of ZF reactant with aperfluorocyclic ketone will produce some amounts of the ZF adducts;however, generally, for best results, the molar ratio of ZF reactant toketone reactant should be kept at about the stoichiometric, i.e., about1:1. The use of a substantial excess of ZF End productl-hydrofluorocyclopropyl acrylate l-hydroperfluorocyclobutyl acrylatel-hydroperfluorocyclobutyl methacrylate l-hydroperfluorocyclopentylmethacrylate reactant will not deleteriously affect the reaction but isto be avoided because unreacted ZF reactant in the product mixture isrelatively difficult to remove from ketone reactant will, of course,result in a proportionate decrease in conversion of the ketone to thedesired ZF adduct. If complete utilization of the ZF reactant isdesired, the molar ratio may be as low as 0.1-l mole of ZF reactant permole of ketone. Generally, the preferred molar ratio of ZF reactant toketone reactant is 0.81 .2: 1.

As indicated hereinbefore, the ZF reactant may be KF, CsF, AgF or RbF.For reasons of economics, KF is preferred.

Reaction temperatures can be between about 0 C.

and the boiling point of the lowest boiling component wherein theboiling point of the lowest boiling component of the reaction mixture isbelow this range, e.g., as is the case with perfluorocyclopentanone(b.p.

the sought-for ZF adduct product. Use of an excess of 2324 C.); thereaction may be carried out within the above indicated temperature rangeby merely bubbling this reactant in gaseous phase into a vigorouslystirred suspension of the ZF reactant in a solvent. Alternatively, thelow boiling reactant may be added and reacted as a liquid by operatingat temperatures below its boiling point.

From the standpoint of convenience, the reaction is carried out underatmospheric pressure. The reaction,-

however, can be carried out under superatmospheric pressure, which isadvantageous in cases wherein the more volatile ketone reactants areemployed.

When a stoichiometric or less than a stoichiometric amount of ZFreactant is employed, the reaction may be assumed to be complete when itis observed that essentially all of this reactant has gone intosolution.

The ZF adducts of the perfluorocyclic ketones may be isolated byconventional methods, such as by evaporating off the solvent undervacuum. This is not absolutely necessary, however, as further reactionof the ZF adducts can be effected, as is, in the solvent solution,without isolating the ZF adducts.

EXAMPLE 9 To a one-necked 25 ml. flask, fitted with a reflux condenserand a thermometer, was added a mixture of 7.0 g. (0.17 mole) ofanhydrous acetonitrile, 15 g. (0.025 mole) of anhydrous KF and 7.0 g.(0.025 mole) of perfluorocyclohexanone. The resulting mixture was heatedto about 55 C. and maintained at that temperature for a period of aboutone hour. At the end of this period the resulting pro duct mixture wascooled to about room temperature and the volatile organic materialremoved under vacuum. There remained in the flask 8.0 g. (0.024 mole, 92percent yield) of a white crystalline solid, identified as a compound ofthe formula:

Analysis:

Calculated for C F OK: F, 62.20; C, 21.43. Found: F, 61.2; C, 19.9. Theinfrared absorption spectrum of the product showed strong absorption at8.5 microns (CF), 10.1

microns and at 10.4 microns, with no absorption peaks in the 5.5-5.9micron region (C O stretch), thus substantiating the expected structure.

EXAMPLES l01 4 The procedure described in Example 9 is repeated,excepting that starting materials, solvents and end products are variedas indicated in the following-table and those ketone reactants withboiling'points below about 55 C. are added in vaporous state by bubblingthe same into a stirred suspension of the ZF reactant in the indicatedsolvent.

TABLE ll Ketone ZF End Example Reactant Reactant Solvent Product 10Perfluorocyclo- CsF nitro- 2 F2 propanone benzene F2 1 l PerfluorocyclolKF dimethylor F butanone formamide E2 l2 Perfluorocyclo- AgF diglyme FlF:

(l A l hutanonc l- H v. ["1- l3 Pcrfluorocyclo- KF tctrumclhyl- \l Uh I"pentanone ene F2 sulfone l 14 Pcrfluorocyclo- F F RbF butyro- 2 hexanonelactone PREPARATION OF THE PERFLUORXNATED ACRYLIC MONOMERS Theperfluorinated acrylic monomers are prepared by reacting acrylylchloride or methacrylyl chloride, hereinafter referred to as acidchloride reactant, with either the isolated ZF adduct of theperfluorocyclic ketone or with the non-isolated ZF adduct, still insolution with the chosen solvent, preferably, for reasons in- 0 dicatedhereinbefore, under essentially anhydrous conexothermic and rate ofaddition of the reactant should be regulated to control the reaction andavoid loss of materials.

The esterification reaction will proceed at temperatures as high as thereflux temperature of the solvent present, if any, or at temperaturesbelow C.; however, no particular advantage accrues from operation atthese extremes. It has been'found that excellent results are obtainedwhen the reaction is carried out between about 20-25 C.

Due to the ready reactivity of the acid chloride reactant with the ZFadducts, no catalysts are required but such may, of course, be used ifdesired. In any event, a conventional polymerization inhibitor, such ashydroquinone, should be employed to avert undesirable prematurepolymerization.

EXAMPLE To a three-necked 100 ml. flask, fitted with a reflux condenser,thermometer, stirrer and dropping funnel, was added a mixture of 45 g.of anhydrous acetonitrile, 9.3 g. (0.16 mole) of anhydrous KF and 44 g.(0.19 mole) of p'erfluorocyclohexanone. The reaction flask contents wereheated to about 50 C. and maintained at that temperature for a period ofabout one hour. At the end of this period the mixture was cooled toabout C. and 14.5 g. (0.16 mole) of acrylyl chloride were slowly addedover a period of about %1 hr. During addition of the acrylic reactant,cooling means were employed to maintain the reaction temperature atabout C. A white precipitate of by-product potassium chloride was formedas the acrylyl chloride was added. The product mixture was washed anumber of times with water to remove unreacted KF and by-product KCl.From the washing there were recovered about 39 g. of a viscous oil whichwas distilled through a small spinning band column. From thedistillation, 36 g. (0.10 mole, 53 percent yield) of a water-whiteliquid, identified as perfluorocyclohexyl acrylate, b.p. 64 C./37 mm.,were collected.

Analysis:

Calculated for C H F O F, 59.37; H, 0.85.

Found: F, 58.0; H, 0.90.

Infrared spectrographic analysis was consistent with the expectedstructure.

EXAMPLE 16 To a three-necked 100 ml. flask, fitted with a refluxcondenser, thermometer, stirrer and dropping funnel and gas inlet tube,containing a mixture of 40 g. of anhydrous acetonitrile and 12 g. (0.21mole) of anhydrous KF at about room temperature, were slowly added 43 g.(0.19 mole) of perfluorocyclopentanone. The reaction was slightlyexothermic and was accompanied by approximately a 10 C. rise intemperature. The resulting mixture was cooled to about 20 C., followingwhich there were slowly added 17 g. (0.19 mole) of acrylyl chloride.During addition of the acrylyl chloride there was formed a whiteprecipitate of KC]. The resulting product mixture was washed a number oftimes with water to remove unreacted KF and byproduct KCl. Thereremained in the reaction vessel 47 g. of a viscous oil which wasdistilled through a small spinning band column to yield 34 g. (0.11mole, 58 percent yield) of a water-white liquid identified asperfluorocyclopentyl acrylate, b.p. 59-61C./58 mm. Analysis:

Calculated for C H F O F, 56.62; H, 0.99. Found: F, 57.5; H, 1.1.Infrared spectrographic analysis confirmed the expected structure.

EXAMPLES 17-21 In the following examples listed in Table 111, the ZF endproducts of Examples 10-14, respectively, are reacted with acrylylchloride or methacrylyl chloride at about 20C. or below depending uponthe thermal stability of the particular ZF adduct employed. Theperfluorinated acrylic products are worked up substantially as describedin Examples 15 and 16.

TABLE I11 ZF Reactant Acid (End Product Chloride Perfluorinated AcrylicProduct Example of Example Reactant 17 1O AcrylylPerfluorocyclopropylacrylate chloride 18 11 Acrylyl Perfluorocyclobutyl acrylate chloride 1912 Methacrylyl Perfluorocyclobutyl methacrylatc chloride 20 13Methacrylyl Perfluorocyclopentyl methacrylate chloride 21 14 MethacrylylPerfluorocyclohexyl methacrylate chloride THE POLYMERIZATION REACTIONThe polymerization reaction may be carried out by any conventionalmethod as described heretofore. For example, polymerization may beeffected in bulk using some form of light or catalyst. Solutionpolymerization can be carried out employing fluorinated solvents, suchas trifluoroethyl trifluoroacetate and an initiator.

The preferred method of polymerization is in aqueous emulsion. Dependentupon the conditions of the polymerization, the polymer can be obtainedas a clear, transparent emulsion in a coagulated form, or as a mixtureof coagulated polymer and emulsion. Coagulation can be effected by theaddition of a number of conventional materials, such as methanol,acetone, any of the well known ionic or cationic salts, e.g., sodiumlauryl sulfate and various fluorinated materials, such as the KF salt ofperfluorosulfonic acid. The emulsions may be easily used to apply thinfilms of the polymers to various surfaces by conventional methods,including the procedure, for example, of coating, as by brushing ordipping, and air-drying.

Suitable polymerization catalysts or initiators are illustrated by freeradical generators, such as light; organic peroxides such as benzoylperoxide, lauryl peroxide, acetyl peroxide, succinyl peroxide,azobutyronitrile and potassium persulfate and inorganic peroxides suchas hydrogen peroxide or sodium peroxide.

Initiation of polymerization by actinic radiation (light) is normallyaccomplished by placing the monomers in an evacuated, sealed tube andthen exposing the tube to a light source, preferably ultraviolet light,at temperatures ranging from about room temperature to about 125 C.

The reaction time for the polymerization varies over a wide range andfor the most part is dependent both upon the temperature employed andupon the nature of the free-radical initiator, or the intensity of theactinic radiation, whichever may be the case. Normally polymerizationcatalyzed by actinic radiation is accomplished in about -72 hours. Whenorganic catalysts are employed, polymerization may be accomplishedwithin a period of about 1-10 hours.

Polymerization can be recognized by observing the formation of a rubberyor hard, tacky material or by observing coagulation or formation of anemulsion out of solution.

EXAMPLE 22 To a three-necked 50 ml. flask, equipped with a droppingfunnel, a stirrer, thermometer and a reflux condenser, were added 18 g.of deionized water, 0.30 g. of sodium lauryl sulfate and 0.05 g. ofpotassium persulfate. After flushing the flask contents with nitrogen,10.0 g. of l-hydroperfluorocyclohexyl acrylate were added. Thetemperature of the reaction vessel contents was raised to 50-55 C. andwas maintained within that range for a period of about 2 1% hours. Atthe end of this period, an additional 0.05 g. of potassium persulfatewere added and heating within the indicatedtemperature range wascontinued. Within ,5 hour from this point polymerization occurred, aswas observed by the formation of a tacky mass in the reaction vessel;The polymeric mass was washed with water and methanol and was then driedunder vacuum. Approximately 7 g., 70 percent yield of the polymer wereobtained. The polymer was found to be insoluble in CF,CICFC1,,

and soluble in CF CI-I CO CF EXAMPLE 23 To the identical apparatusemployed in Example 22, were added 18 g. of deionized water, 0.30 g. ofsodium lauryl sulfate and 0.05 g. of potassium persulfate. Afterflushing the flask contents with nitrogen, 10.0 g. oflhydroperfluorocyclopentyl acrylate were added. The temperature of thereaction vessel contents was raised to 50-5 5 C. and was maintainedwithin that range for a period of about 2 hours. At the end of thisperiod, an additional 005 g. of potassium persulfate were added andheating within the indicated temperature range was continued. Within /2hour from this point polymerization occurred as was observed by theformation of a mixture of a latex and coagulated material. The polymericmass was washed with water and methanol and was then dried under vacuum.Approximately 8 g., percent yield of a water-white, rubbery and somewhattacky polymer were recovered.

EXAMPLE 24 To the identical apparatus employed in Example 22 were added15.0 g. of deionized water, 0.09 g. of ammonium perfluorooctanoate and0.014 g. of potassium persulfate. After flushing the flask contents withnitrogen, 2.2 g. of l-hydroperfluorocyclohexyl acrylate were added. Thetemperature of the reaction vessel contents was raised to 55 C. andmaintained at that temperature for a period of about onc hour duringwhich time polymerization occurred, as evidenced by the formation of atransparent latex dispersion.

EXAMPLE 25 To the identical apparatus employed in Example 22 were added2.5 g. of perfluorocyclohexyl acrylate, 15.0 g. of deionized water, 0.09g. of sodium lauryl sulfate and 0.014 g. of potassium persulfate. Thereaction flask contents were flushed with nitrogen and the reactionflask contents were heated to 50-55 C. Within one hour polymerizationoccurred, as evidenced by the formation of a tacky mass in the reactionvessel. The polymeric mass was washed with water and methanol and wasthen dried under vacuum. Approximately 2.0 g. of polymer were recovered.The polymer was found to be insoluble in CF ClCFCl and CF CFCICCI CF andsoluble in trifluoroethyltrifluoroacetate andlmethoxy-2-chlorooctafluorocyclohexene.

EXAMPLE 26 To the identical apparatus employed in Example 22 were added5.0 g. of perfluorocyclopentyl acrylate, 30.0 g. of deionized water,0.18 g. of sodium lauryl sulfate and 0.028 g. of potassium persulfate.After flushing of the reaction flask contents with nitrogen, thetemperature in the reaction vessel was raised to about 50 C. andmaintained at that level for about two hours. During this periodpolymerization occurred, as evidenced by the formation of a tacky massin the reaction vessel. The resulting polymeric mass was washed withwater and methanol and was then dried under vacuum. Approximately 4.5 g.of a clear, rubbery polymer were obtained.

When the polymerization procedures described in Examples 22-26 arerepeated, employing other fluorinated acrylic monomers within the scopeof the invention, such as those listed under the fluorinated acrylateproduct column of Table III, alone, or in admixture with otherpolymerizable monomers as hereinbefore described", as in the case ofExamples 22-26, polymeric products are formed.

UTILITY OF THE POLYMERIC PRODUCTS The homopolymeric products may be usedto impart oil and water repellent properties to a variety of porousmaterials, such as textiles, by applying the same as coatings to suchmaterials, such as by spraying, brushing or clipping procedures. Thepolymer may be applied as an aqueous emulsion or in solution with asuitable solvent, followed by drying of the coated material to removewater or the solvent.

In the following examples, the so-called 3M Oil Repellency Test" wasused to evaluate the oil repellent properties of a cotton fabric treatedwith representative homopolymeric products. This test was performed asdescribed by EJ. Grajeck et al., Textile Research Journal, April 1962,pp. 323-324. Water repellency was evaluated by the Spray Test Method(ASTM-D583- 58).

EXAMPLE 27 Samples of 80 X 80 inch undyed cotton print cloth were dippedinto a solution comprising 2 percent by weight of thel-hydroperfluorocyclopentyl acrylate polymer, prepared in Example 23, intrifluoroethyl trifluoroacetate solvent. The cloth samples were blottedwith paper toweling to remove excess solution and were then dried in anoven at 160 C. for five minutes. The oil repellency, as measured by the3M Oil Repellency Test, received a rating of 70. The water repellency,as measured by the Spray Test Method, also received a rating of 70.

EXAMPLE 28 The polymeric latex dispersion obtained from I-hydroperfluorocyclohexyl acrylate, obtained as described in Example 24,was diluted with water so as to give an emulsion possessing aconcentration of 2.5 percent by weight solids. Samples of 80 X 80 inchundyed cotton print cloth were dipped into the emulsion, blotted withpaper toweling and then dried in an oven at 160 C. for five minutes.Both the oil repellency rating and spray rating were 70.

When other polymers within the scope of the invention are used to formcoatings on cotton and other fabrics, substantially the same results areobtained, i.e., there is imparted to such materials good oil and waterrepellent properties.

The homopolymeric products may also be used to cast elastic,transparent, thermoplastic films by conventional procedures, such as bycasting a solution of the polymeric product in a suitable solvent over asmooth surface, evaporating the solvent therefrom, drying the resultingfilm and stripping the same from the smooth surface. Such films may alsobe prepared by casting solutions of the corresponding monomers over thesmooth surface in a suitable solvent, evaporating the solvent, dryingthe resulting film and polymerizing in situ by means of heat and smallamounts ofa conventional initiator.

oand heteropolymers may be prepared by procedures well known to the artby polymerizing mixtures of monomers according to the invention andother polymerizable monomers with heat, in the presence of conventionalcatalysts to yield resins reflecting properties contributed by each ofthe monomers employed. Depending upon the choice of monomers, suchresins may be either of a thermoplastic or thermosetting nature.

The foregoing description is to be taken as illustrative only and theinvention is to be limited only by the scope of the appended claims.

We claim:

1. Fluorinated acrylic compounds of the formula:

wherein R, is a perfluorinated alkylene radical containing from two tofive carbon atoms, X is a member selected from the group consisting of Hand F and Y is a member selected from the group consisting of H and CH2. Fluorinated acrylic compounds according to claim 1 wherein R,contains four to five carbon atoms.

3. Fluorinated acrylic compounds according to claim 2 wherein X is H.

4. Fluorinated acrylic compounds according to claim 2 wherein X is F.

5. Perfluorocyclopentyl acrylate.

6. Perfluorocyclohexyl acrylate.

7. Perfluorocyclohexyl methacrylate.

8. l-Hydroperfluorocyclopentyl acrylate.

9. l-Hydroperfluorocyclohexyl acrylate.

10. l-Hydroperfluorocyclopentyl methacrylate.

2. Fluorinated acrylic compounds according to claim 1 wherein Rfcontains four to five carbon atoms.
 3. Fluorinated acrylic compoundsaccording to claim 2 wherein X is H.
 4. Fluorinated acrylic compoundsaccording to claim 2 wherein X is F.
 5. Perfluorocyclopentyl acrylate.6. Perfluorocyclohexyl acrylate.
 7. Perfluorocyclohexyl methacrylate. 8.1-Hydroperfluorocyclopentyl acrylate.
 9. 1-Hydroperfluorocyclohexylacrylate.
 10. 1-Hydroperfluorocyclopentyl methacrylate.